Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/417—Polyolefins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/423—Polyamide resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
  • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
  • H01M50/491—Porosity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a separator for a nonaqueous electrolyte battery and a nonaqueous electrolyte battery using the same.
• non-aqueous electrolyte batteries such as lithium ion secondary batteries have been widely used as power sources for portable electronic devices and transportation devices.
• they are lightweight and have high energy density, they can be used as high-output power sources for driving vehicles. Demand expansion is expected.
• the non-aqueous electrolyte battery is disposed in the cell so that the positive electrode and the negative electrode face each other, and has an ion-permeable separator between both electrodes in order to prevent short-circuiting of both electrodes.
• a polyolefin porous membrane is preferably used as the separator.
• a polyolefin porous membrane is excellent in electrical insulation, ion permeability, electrolytic solution resistance and oxidation resistance.
• the polyolefin porous membrane can block the current at a temperature of about 100 to 150 ° C. assumed at the time of abnormal temperature rise, thereby blocking the current and suppressing excessive temperature rise. However, if the temperature continues to increase even after the pores are closed for some reason, the polyolefin porous membrane contracts, causing a short circuit between the electrodes, which may cause the nonaqueous electrolyte battery to ignite.
• separator that can constitute a non-aqueous electrolyte battery excellent in safety, a porous resin film having a thermoplastic resin as a main component and a heat shrinkage rate at 150 ° C. of 10% or more, and heat-resistant fine particles Separator for non-aqueous electrolyte battery having heat-resistant porous layer contained therein (for example, see Patent Document 1), separator for non-aqueous electrolyte secondary battery in which a porous film of water-soluble polymer and a porous film of polyolefin are laminated (For example, refer to Patent Document 2), a separator for a lithium ion battery having a coating layer formed by a slurry composition containing a polymer microporous membrane, inorganic fine particles, water-soluble polymer, water-insoluble organic fine particles, and water (for example, Patent Document 3), lithium ion battery separator having a layer containing a heat-resistant nitrogen-containing aromatic polymer and ceramic powder (for example, Patent reference 4)
• an object of the present invention is to provide a separator for a nonaqueous electrolyte battery that is excellent in shape stability in a temperature range of 160 to 200 ° C.
• a porous membrane (I) containing a polyolefin resin Nonaqueous electrolyte battery separator having an inorganic filler, a water-soluble polymer containing a structure represented by the following general formula (1), a water-insoluble polymer and a porous layer (II) containing a basic compound:
• R 1 and R 2 each independently represent a hydroxyl group, a carboxyl group or a sulfonic acid group;
• R 3 and R 4 each independently represent a halogen, a nitro group or a monovalent group having 1 to 10 carbon atoms.
• a and b each independently represent an integer of 1 or more, c and d each independently represent an integer of 0 or more; provided that a + c and b + d each independently represent an integer of 1 to 4;
• n 1 represents an integer of 0 to 3;
• X 1 represents a single bond, CH 2 , SO 2 , CO, O, S, C (CH 3 ) 2 or C (CF 3 ) 2 .
• the present invention also includes a non-aqueous electrolyte battery in which a positive electrode and a negative electrode are laminated via a separator, and the separator is the above-described separator for a non-aqueous electrolyte battery.
• the battery separator of the present invention is excellent in shape stability in a temperature range of 160 to 200 ° C.
• the nonaqueous electrolyte battery separator of the present invention includes a porous membrane (I) containing a polyolefin resin, an inorganic filler, a water-soluble polymer containing a structure represented by the general formula (1), and a water-insoluble solution. And a porous layer (II) containing a basic polymer and a basic compound. It is preferable to have the porous layer (II) on one side or both sides of the porous membrane (I).
• having the porous layer (II) on one surface of the porous membrane (I) means that the porous layer (II) is formed on one surface of the porous membrane (I).
• having porous layer (II) on both surfaces of porous membrane (I) means that porous layer (II) is formed on both surfaces of porous membrane (I). Details of the present invention will be described below.
• Porous membrane (I) The porous membrane (I) in the present invention contains a polyolefin resin. Since the porous membrane (I) contains a polyolefin resin, the porous membrane (I) has a function of blocking current at the time of abnormal temperature rise, thereby blocking current and preventing a short circuit between both electrodes in the nonaqueous electrolyte battery.
• polystyrene resin examples include polyethylene resin and polypropylene resin. Two or more of these may be included. Among these, polyethylene resin is preferable because of its higher electrical insulation, ion permeability, and pore blocking effect.
• the porous membrane (I) may contain other resins together with the polyolefin resin.
• the melting point (softening point) of the resin constituting the porous membrane (I) is preferably 150 ° C. or less, preferably 140 ° C. or less, from the viewpoint of the function of closing the pores when the temperature rises abnormally in the charge / discharge reaction (hole closing function). More preferred is 130 ° C. or lower.
• the melting point (softening point) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher, from the viewpoint of suppressing pore blockage during normal operation.
• the melting point (softening point) can be determined by differential scanning calorimetry (DSC) based on JIS K7121: 2012.
• the weight average molecular weight of the polyolefin resin is preferably 300,000 or more from the viewpoint of process workability and mechanical strength (for example, tensile strength, elastic modulus, elongation, piercing strength) that can withstand various external pressures that occur during winding with the electrode. More preferably, it is 400,000 or more, More preferably, it is 500,000 or more.
• the pore diameter of the porous membrane (I) is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and even more preferably 0.1 ⁇ m or more from the viewpoint of securing ion permeability and suppressing deterioration of battery characteristics.
• 1.0 ⁇ m or less is preferable, 0.5 ⁇ m or less is more preferable, and 0.3 ⁇ m or less is more preferable from the viewpoint of increasing the response to the temperature of the pore closing function.
• the air permeability resistance of the porous membrane (I) is preferably 500 s / 100 cc Air or less, more preferably 400 s / 100 cc Air or less, and further preferably 300 s / from the viewpoint of securing ion permeability and suppressing deterioration of battery characteristics. In order to obtain sufficient insulation in the battery, it is preferably 50 s / 100 cc Air or more, more preferably 70 s / 100 cc Air or more, and further preferably 100 s / 100 cc Air or more.
• the air resistance can be determined by a Gurley type densometer type B manufactured by Tester Sangyo Co., Ltd. based on JIS P8117: 2009.
• Porous layer (II) The porous layer (II) has a function of improving the shape stability of the separator during heating.
• the porous layer (II) contains an inorganic filler, a water-soluble polymer containing a structure represented by the general formula (1), a water-insoluble polymer, and a basic compound. Other components may be included as necessary.
• the porous layer (II) is a slurry containing an inorganic filler, a water-soluble polymer containing a structure represented by the general formula (1), a water-insoluble polymer, a basic compound and a solvent as essential components, This can be formed on the porous layer (I) by coating and drying.
• the solvent used for the slurry is water, a small amount of alcohols may be added from the viewpoints of drying properties and coatability to the porous layer (I). Below, the detail of each component is demonstrated.
• porous layer (II) has an effect of improving the shape stability during heating of the separator by including the inorganic filler.
• an inorganic filler is an inorganic filler generally called a filler.
• an inorganic filler selected from alumina and boehmite is preferable.
• Alumina and boehmite have high hydrophilicity on the particle surface, and can be firmly bound to the inorganic filler and the water-soluble polymer by adding a small amount.
• the average particle size of the inorganic filler is preferably 0.1 ⁇ m or more. If the average particle size is 0.1 ⁇ m or more, the specific surface area of the inorganic filler can be moderately suppressed and the surface adsorbed water can be reduced, so that the moisture content as a separator can be reduced and the battery characteristics can be further improved. Is possible.
• the average particle size of the inorganic filler is preferably 2.0 ⁇ m or less, and more preferably 1.0 ⁇ m or less. When the average particle size is 2.0 ⁇ m or less, the film thickness of the porous layer (II) can be easily adjusted to a desired range described later.
• the average particle size referred to here is a laser scattering particle size distribution meter ("MT3300EXII” manufactured by Microtrack Bell Co., Ltd. (formerly Nikkiso Co., Ltd.)), and a liquid flow rate obtained by adding an inorganic filler to water.
• the particle size (D50) of 50% in the volume-based integrated fraction measured within 10 minutes after being circulated for 3 minutes while irradiating ultrasonic waves under the conditions of 45% and output of 25W.
• the water-soluble polymer has an effect of improving the shape stability of the separator during heating by binding inorganic fillers together. Since the water-soluble polymer including the structure represented by the following general formula (1) has a rigid main chain structure, the heat resistance can be improved.
• R 1 and R 2 in the general formula (1) have an acidic functional group selected from a hydroxyl group, a carboxyl group, and a sulfone group, thereby forming an ionic bond with the basic compound, through which an inorganic filler is formed. Tightly bind. Due to these effects, the shape stability of the separator during heating can be improved.
• the water solubility in the water-soluble polymer is expressed in the presence of the structure represented by the general formula (1) and a basic compound.
• R 1 and R 2 each independently represent a hydroxyl group, a carboxyl group, or a sulfonic acid group.
• R 3 and R 4 each independently represent a halogen, a nitro group, or a monovalent organic group having 1 to 10 carbon atoms.
• a and b each independently represent an integer of 1 or more, and c and d each independently represents an integer of 0 or more.
• a + c and b + d each independently represent an integer of 1 to 4.
• n 1 represents an integer of 0 to 3.
• X 1 represents a single bond, CH 2 , SO 2 , CO, O, S, C (CH 3 ) 2 or C (CF 3 ) 2 .
• R 1 and R 2 are preferably a hydroxyl group or a carboxyl group, and c and d are preferably 0.
• water-soluble polymer a polymer selected from polyimide, polyamide and polyamideimide is preferable, and the heat resistance can be further improved.
• the water-soluble polymer preferably has a structural unit selected from the structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (3), and can further improve the heat resistance. it can.
• R 5 represents a divalent organic group having 2 to 50 carbon atoms
• R 6 represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms
• m 1 and c 1 are both 0 or 1
• R 7 and R 8 each independently represents a divalent organic group having 2 to 50 carbon atoms.
• R 6 in the general formula (2) and R 8 in the general formula (3) may have either an aromatic skeleton or an aliphatic skeleton.
• the water solubility of the polymer is improved, and the amount of the basic compound that is a water solubilizer can be reduced.
• R 5 and R 7 in the general formulas (2) and (3) is a diamine residue represented by the general formula (1), which binds the inorganic filler more firmly. By wearing it, the shape stability during heating can be further improved.
• the water-soluble polymer includes only one of the structural unit represented by the general formula (2) and the structural unit represented by the general formula (3), any one of R 5 and R 7 is used. It is preferable that 50 mol% or more of these is a diamine residue represented by the general formula (1).
• the water-soluble polymer includes both the structural unit represented by the general formula (2) and the structural unit represented by the general formula (3), 50 mol% or more of the total of R 5 and R 7 is represented by the general formula ( It is preferable that it is a diamine residue represented by 1), and it is more preferable that 50 mol% or more of each of R 5 and R 7 is a diamine residue represented by the general formula (1).
• the water-soluble polymer is polyimide.
• Polyimide is an imide cyclized product of polyamic acid, which is a polycondensate of diamine and tetracarboxylic dianhydride, and includes a diamine residue and a tetracarboxylic dianhydride residue.
• R 5 represents a diamine residue
• R 6 represents a tetracarboxylic dianhydride residue.
• Examples of the diamine having the structure represented by the general formula (1) include 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 5,5′-methylenebis (2-aminobenzoic acid), bis (3-amino-4-carboxyphenyl) sulfone, 2,2-bis (3-amino-4-carboxyphenyl) propane, 2,2-bis (3-amino-5-carboxyphenyl) propane, 2,2- Bis (4-amino-3-carboxyphenyl) propane, 2,2-bis (3-amino-4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-amino-5-carboxyphenyl) hexafluoropropane 2,2-bis (4-amino-3-carboxyphenyl) hexafluoropropane, bis (3-amino-4-carboxyphenyl) ether, 1-4 hydrogen atoms of these compounds, hydroxyl group, and the like
• diamines not containing the structure represented by the general formula (1) examples include paraphenylene diamine, metaphenylene diamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, and 3,4′-diaminodiphenyl ether.
• 4,4′-diaminodiphenylmethane 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (trifluoromethyl) benzidine, 9,9'-bis (4-aminophenyl) fluorene, hexamethylenediamine 1,3-bis (3-aminopropyltetra Chill disiloxane), and the like. Two or more of these may be used.
• tetracarboxylic dianhydrides include 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4 , 9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-paraterphenyl tetracarboxylic dianhydride, 3,3 ′, 4,4′-metaterphenyl tetra Aromatic tetracarboxylic anhydrides such as carboxylic dianhydrides, 1,3,3a, 4,5,9b-hexahydro-5 (te
• R 6 preferably has an aliphatic skeleton.
• aliphatic skeleton refers to a skeleton containing an acyclic or cyclic non-aromatic hydrocarbon.
• the acid dianhydride that gives R 6 which is preferable as the aliphatic skeleton include the above-described aliphatic tetracarboxylic acid anhydrides, or 1 to 4 hydrogen atoms of these compounds substituted with a hydroxyl group, a carboxyl group or a sulfonic acid group. The thing which was done is mentioned. Two or more of these may be used.
• the polyimide having the structural unit represented by the general formula (2) is obtained by polycondensation of the above-described diamine and tetracarboxylic dianhydride in a solvent to obtain polyamic acid and then imide cyclization. Can be obtained.
• the charge ratio (molar ratio) of tetracarboxylic dianhydride and diamine is preferably 100: 50 to 150.
• the terminal of the polyimide is dicarboxylic anhydride such as maleic anhydride, phthalic anhydride, nadic anhydride, ethynyl phthalic anhydride, hydroxyphthalic anhydride; or hydroxyaniline, aminobenzoic acid, dihydroxyaniline, carboxyhydroxyaniline. It can also be sealed with a monoamine such as dicarboxyaniline.
• the solvent used in the polycondensation reaction is not particularly limited as long as the produced polyamic acid can be dissolved.
• N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N— Aprotic polar solvents such as dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylimidazoline; phenol solvents such as phenol, m-cresol, chlorophenol, nitrophenol; polyphosphoric acid, phosphoric acid A phosphorus-based solvent to which phosphorus pentoxide is added can be preferably used.
• polyamic acid which is a polyimide precursor
• polyimide precursor is obtained by reacting diamine and tetracarboxylic dianhydride in these solvents at a temperature of 100 ° C. or lower.
• imide cyclization is preferably performed in a temperature range of 100 ° C. to 300 ° C. to obtain a polyimide resin.
• bases such as triethylamine, isoquinoline, and pyridine can be added as a catalyst, and water produced as a by-product is mixed with a nonpolar solvent such as toluene and azeotroped to proceed with removal. You can also.
• the solid of polyimide can be obtained by throwing the reaction solution into water or the like to precipitate polyimide and drying it. Also, in the state of polyamic acid, it is once poured into a poor solvent such as water to obtain a polyamic acid solid, which is heat-treated at a temperature of 100 ° C. to 500 ° C. to perform imide cyclization, thereby solidifying the polyimide resin. You can also get
• the water-soluble polymer is polyamideimide.
• Polyamideimide is an imide cyclized product of polyamideamidic acid that is a polycondensate of diamine and tricarboxylic acid, and includes a diamine residue and a tricarboxylic acid residue.
• R 5 represents a diamine residue
• R 6 represents a tricarboxylic acid residue.
• diamine examples include those exemplified above as the diamine constituting the polyimide.
• tricarboxylic acids include aromatic compounds such as trimellitic acid, hydroxytrimellitic acid, diphenyl ether tricarboxylic acid, diphenyl sulfone tricarboxylic acid, dicyclohexyl ether tricarboxylic acid, dicyclohexyl sulfone tricarboxylic acid, dicyclohexyl ether tricarboxylic acid, bicyclohexyl tricarboxylic acid, etc.
• aromatic compounds such as trimellitic acid, hydroxytrimellitic acid, diphenyl ether tricarboxylic acid, diphenyl sulfone tricarboxylic acid, dicyclohexyl ether tricarboxylic acid, dicyclohexyl sulfone tricarboxylic acid, dicyclohexyl ether tricarboxylic acid, bicyclohexyl tricarboxylic acid, etc.
• R 6 preferably has an aliphatic skeleton from the viewpoint of reducing the necessary addition amount of a basic compound that is a water-solubilizing agent and suppressing internal resistance during battery production.
• aliphatic skeleton refers to a skeleton containing an acyclic or cyclic non-aromatic hydrocarbon.
• examples of the tricarboxylic acid that gives R 6 which is preferable as the aliphatic skeleton include the above-described aliphatic compounds, acid anhydrides thereof, and phenol-substituted products of these compounds. Two or more of these may be used.
• these tricarboxylic acids and dicarboxylic acids such as phthalic acid and hydroxyphthalic acid or their anhydrides; other tricarboxylic acids such as trimesic acid or their anhydrides; or pyromellitic acid, diphenyl ether tetracarboxylic acid, diphenyl A tetracarboxylic acid such as sulfonetetracarboxylic acid, biphenyltetracarboxylic acid, or a hydroxy-substituted product thereof, or an anhydride thereof may be copolymerized.
• the amount is preferably 50 mol% or less based on the total amount of the acids and acid anhydrides.
• the polyamideimide having the structural unit represented by the general formula (2) is obtained, for example, by polycondensation of the above-described diamine and tricarboxylic acid in a solvent to obtain polyamideamidic acid and imide cyclization. Can do.
• the charging ratio (molar ratio) of tricarboxylic acid and diamine is preferably 100: 50 to 150.
• the ends of polyamideimide can be sealed.
• Examples of the solvent used in the polycondensation reaction include those exemplified as the solvent used in the polycondensation reaction of polyimide.
• polyamic acid which is a polyamideimide precursor
• polyamideimide precursor is obtained by reacting diamine and tricarboxylic acid in these solvents at a temperature of 100 ° C. or lower.
• imide cyclization is preferably performed in a temperature range of 100 ° C. to 300 ° C. to obtain a polyamideimide resin.
• bases such as triethylamine, isoquinoline, and pyridine can be added as a catalyst, and water produced as a by-product is mixed with a nonpolar solvent such as toluene and azeotroped to proceed with removal. You can also.
• the polyamideimide is precipitated by introducing the reaction solution into water or the like and dried to obtain a polyamideimide solid. Also, in the state of polyamic acid, it is once poured into a poor solvent such as water to obtain a polyamic acid solid, which is heat-treated at a temperature of 100 ° C. to 500 ° C. to perform imide cyclization, A solid can also be obtained.
• the polyamide having the structural unit represented by the general formula (3) is a polycondensate of diamine and dicarboxylic acid.
• R 7 represents a diamine residue
• R 8 represents a dicarboxylic acid residue.
• diamines examples include those exemplified above as diamines constituting polyimide.
• dicarboxylic acids examples include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid and other aromatic dicarboxylic acids, cyclohexane dicarboxylic acid, dicyclohexyl ether dicarboxylic acid, dicyclohexyl sulfone dicarboxylic acid, bicyclohexyl dicarboxylic acid And aliphatic dicarboxylic acids such as Two or more of these may be used.
• R 8 preferably has an aliphatic skeleton from the viewpoint of reducing the required addition amount of a basic compound that is a water-solubilizing agent and suppressing internal resistance during battery production.
• aliphatic skeleton refers to a skeleton containing an acyclic or cyclic non-aromatic hydrocarbon.
• dicarboxylic acid that gives R 8 preferable as the aliphatic skeleton include the aliphatic dicarboxylic acids described above. Two or more of these may be used.
• the polyamide having the structural unit represented by the general formula (3) can be obtained, for example, by polycondensing the above-described diamine and dicarboxylic acid in a solvent.
• the charging ratio (molar ratio) of dicarboxylic acid and diamine is preferably 100: 50 to 150.
• Examples of the solvent used in the polycondensation reaction include those exemplified as the solvent used in the polycondensation reaction of polyimide.
• a polyamide is obtained by reacting an acid chloride or active ester of a dicarboxylic acid and a diamine in these solvents at a temperature of 30 ° C. or lower.
• a base such as triethylamine or pyridine can be added as a catalyst.
• the polyamide is precipitated by introducing the reaction solution into water or the like and dried to obtain a polyamide solid.
• the water-soluble polymer has a larger weight average molecular weight within the range where water-solubility is obtained, because the shape stability of the separator during heating can be improved.
• the weight average molecular weight of the water-soluble polymer is preferably 20,000 or more, more preferably 25,000 or more.
• the upper limit with preferable weight average molecular weight is 200,000 or less from a water-soluble viewpoint.
• the weight average molecular weight is a value determined by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
• the weight molecular weight of the water-soluble polymer was measured under the following conditions. 1) Equipment: Waters 2690 2) Column: TOSOH CORPORATION, TSK-GEL (d-4000 & d-2500) 3) Solvent: NMP 4) Flow rate: 0.4 mL / min 5) Sample concentration: 0.05 to 0.1 wt% 6) Injection volume: 50 ⁇ L 7) Temperature: 40 ° C 8) Detector: Waters 996 In addition, the standard polystyrene of Polymer Laboratories was used for the polystyrene used for conversion.
• the content of the water-soluble polymer in the porous layer (II) is preferably 0.4 to 5.0 parts by mass with respect to 100 parts by mass of the inorganic filler.
• content of a water-soluble polymer By making content of a water-soluble polymer into 0.4 mass part or more, an inorganic filler can be firmly bound and the shape stability of the separator at the time of a heating can be improved more.
• by setting the content of the water-soluble polymer to 5.0 parts by mass or less clogging of the porous membrane (I) can be reduced, and an increase in the air resistance of the separator can be suppressed.
• Water-insoluble polymer has an effect of suppressing the detachment of the porous layer (II) from the porous membrane (I).
• the water-insoluble polymer is preferably an electrochemically stable material that has electrical insulation properties, is stable with respect to a non-aqueous electrolyte, and is hardly oxidized or reduced in the battery operating voltage range.
• electrochemically stable material examples include styrene resin [polystyrene (PS), etc.], styrene-butadiene rubber (SBR), acrylic resin (PMMA, etc.), polyalkylene oxide [polyethylene oxide (PEO), etc.], fluororesin (PVDF) Etc.), and derivatives thereof.
• PS polystyrene
• SBR styrene-butadiene rubber
• acrylic resin PMMA, etc.
• PEO polyalkylene oxide
• PVDF fluororesin
• styrene resin, acrylic resin, and fluororesin are preferable, and acrylic resin is more preferable. Since the acrylic resin has a low glass transition temperature (Tg) and high flexibility, the detachment of the porous layer (II) from the porous membrane (I) can be more effectively suppressed. Resins with low Tg and high flexibility tend to have low shape stability during heating, but contain the aforementioned water-soluble polymer in the porous layer (II), thereby suppressing softening at high temperatures and heating The detachment of the porous layer (II) from the porous membrane (I) can be further suppressed while improving the shape stability.
• Tg glass transition temperature
• fluororesin fluororesin
• the content of the water-insoluble polymer in the porous layer (II) is preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the inorganic filler.
• the content of the water-insoluble polymer is preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the inorganic filler.
• the basic compound has an effect of improving the binding property with the inorganic filler by forming an ionic bond with the water-soluble polymer including the structure represented by the general formula (1). .
• Examples of the basic compound include alkali metal compounds, alkaline earth metal compounds, quaternary ammonium compounds having 1 to 20 carbon atoms, and amine compounds having 1 to 20 carbon atoms. From the viewpoint of ionic bonding with the water-soluble polymer, one or more compounds selected from alkali metal compounds, quaternary ammonium compounds having 1 to 20 carbon atoms, and amine compounds having 1 to 20 carbon atoms are preferable.
• alkali metal compounds include alkali metal hydroxides, carbonates, and phosphates.
• alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like. Two or more of these may be contained. From the viewpoint of solubility and stability of the water-soluble polymer, a compound selected from lithium hydroxide, sodium hydroxide and potassium hydroxide is more preferable.
• alkali metal carbonates include lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, rubidium bicarbonate, cesium carbonate, cesium bicarbonate, and potassium sodium carbonate. Two or more of these may be used. From the viewpoint of the solubility and stability of the water-soluble polymer, a compound selected from sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and potassium potassium carbonate is more preferred.
• alkali metal phosphates include lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, List potassium dihydrogen phosphate, rubidium phosphate, rubidium hydrogen phosphate, rubidium dihydrogen phosphate, cesium phosphate, cesium hydrogen phosphate, cesium dihydrogen phosphate, sodium potassium phosphate, sodium potassium hydrogen phosphate, etc. Can do. Two or more of these may be used. From the viewpoint of solubility and stability of the water-soluble polymer, a compound selected from sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, sodium potassium phosphate, and sodium potassium hydrogen phosphate is preferable.
• Examples of amine compounds having 1 to 20 carbon atoms include aliphatic tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, and N-methylethanolamine; pyridine, N, N-dimethylamino And aromatic amines such as pyridine and lutidine. Two or more of these may be used.
• quaternary ammonium compounds having 1 to 20 carbon atoms include quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Two or more of these may be used.
• the content of the basic compound in the porous layer (II) is preferably 0.2 molar equivalent or more with respect to the acidic functional group in the water-soluble polymer, from the viewpoint of solubility of the water-soluble polymer. More preferably 5 molar equivalents or more.
• the content of the basic compound exceeds 4 molar equivalents, the internal resistance of the battery increases and the charge / discharge rate may decrease, so the content is preferably 4 molar equivalents or less.
• 3 mol equivalent or less is further more preferable from a viewpoint of suppressing the decomposition
• the porous layer (II) may contain various additives other than those described above, for example, an antioxidant, a preservative, a surfactant and the like, if necessary.
• the film thickness of the porous layer (II) is preferably 1 ⁇ m or more and more preferably 2 ⁇ m or more from the viewpoint of ensuring the film breaking strength and insulation when the porous film (I) is melted and contracted at a melting point or higher.
• the film thickness is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
• the nonaqueous electrolyte battery separator of the present invention has the aforementioned porous membrane (I) and porous layer (II).
• the porous layer (II) is preferably formed on one surface or both surfaces of the porous membrane (I).
• the increase in air permeability of the nonaqueous electrolyte battery separator is preferably +200 s / 100 cc Air or less, and more preferably less than +100 s / 100 cc Air.
• the degree of increase in air permeability is +200 s / 100 cc Air or less, ion permeability can be secured and deterioration of battery characteristics can be suppressed.
• the degree of increase in air permeability refers to the degree of increase in the air resistance of the separator having the porous film (I) and the porous layer (II) relative to the air resistance of the porous film (I) only. It is a value indicating whether or not The air resistance is measured according to JIS P-8117: 2009 using a Gurley type densometer type B manufactured by Tester Sangyo Co., Ltd.
• the porous membrane (I) and the separator can be fixed so that there are no wrinkles between the clamping plate and the adapter plate, the air resistance can be measured, and the air permeability increase can be calculated from the following formula. it can.
• the porous membrane (I) A method for reducing clogging is mentioned.
• the thermal shrinkage of the separator for nonaqueous electrolyte batteries is preferably 5% or less, more preferably less than 3%.
• the heat shrinkage ratio is an index of shape stability during heating. If the heat shrinkage ratio is 5% or less, the positive electrode and the negative electrode are contacted and short-circuited due to the heat shrinkage of the separator even during abnormal battery heat generation. Can be suppressed.
• the heat shrinkage rate refers to the ratio of the length of the separator after heating at a predetermined temperature to the length of the separator at room temperature.
• Examples of means for setting the heat shrinkage rate to 5% or less include a method of adjusting the content of the water-soluble polymer to the above-mentioned preferable range.
• the separator for a nonaqueous electrolyte battery of the present invention includes, for example, the above-mentioned inorganic filler, water-soluble polymer, water-insoluble polymer, base on at least one surface of the porous membrane (I). It can be obtained by applying a coating liquid containing an organic compound and a solvent, and then removing the solvent to form the porous layer (II). Details will be described below.
• the coating solution is prepared by adding an inorganic filler to an aqueous solution in which a water-soluble polymer and a basic compound are dissolved in water, mixing and dispersing the mixture, and then adding a water-insoluble polymer. It is preferable to manufacture by mixing. From the viewpoint of drying properties and coatability to the porous layer (I), a small amount of alcohols may be added to water.
• Examples of the method for mixing and dispersing the inorganic filler include a mechanical stirring method, an ultrasonic dispersion method, a high pressure dispersion method, a media dispersion method, and the like.
• a media dispersion method that can highly disperse the inorganic filler and can blend the inorganic filler and the water-soluble polymer in a short time is preferable.
• Production method of porous membrane (I) examples include a foaming method, a phase separation method, a dissolution recrystallization method, a stretch opening method, and a powder sintering method. It is done. Among these, the phase separation method is preferable from the viewpoint of the uniformity of the fine pores and the cost.
• porous membrane (I) As a method for producing the porous membrane (I) by the phase separation method, for example, polyethylene and a molding solvent are heated, melted and kneaded, and the resulting molten mixture is extruded from a die and cooled to form a gel-like molded product.
• the method include obtaining a porous film by stretching the obtained gel-like molded product in at least a uniaxial direction and removing the molding solvent.
• Examples of the method for applying the coating liquid to the porous membrane (I) include a gravure coater method, a small diameter gravure coater method, a reverse roll coater method, a transfer roll coater method, a kiss coater method, a dip coater method, a knife coater method, an air Examples include a doctor coater method, a blade coater method, a rod coater method, a squeeze coater method, a cast coater method, a die coater method, a screen printing method, and a spray coating method.
• Examples of the method for removing the solvent include a method in which the porous membrane (I) is fixed by heating and drying at a temperature not higher than the melting point, and a method in which the porous membrane (I) is dried under reduced pressure.
• the method by heat drying is preferable because it leads to simplification of the process.
• the heating and drying temperature is preferably 70 ° C. or less, more preferably 60 ° C. or less, and further preferably 50 ° C. or less from the viewpoint of suppressing the expression of the pore closing function of the porous membrane (I) and reducing the amount of heat used. .
• the heat drying time is preferably several seconds to several minutes.
• Nonaqueous Electrolyte Battery The separator for a nonaqueous electrolyte battery of the present invention can be suitably used for a battery using a nonaqueous electrolyte. Specifically, it is preferable as a separator for secondary batteries such as nickel-hydrogen batteries, nickel-cadmium batteries, nickel-zinc batteries, silver-zinc batteries, lithium secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, etc. Can be used. Especially, it is preferable to use as a separator of a lithium ion secondary battery.
• secondary batteries such as nickel-hydrogen batteries, nickel-cadmium batteries, nickel-zinc batteries, silver-zinc batteries, lithium secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, etc.
• a positive electrode and a negative electrode are laminated via a separator.
• the separator contains an electrolytic solution (electrolyte).
• the structure of the electrode is not particularly limited.
• an electrode structure in which a disc-shaped positive electrode and a negative electrode are opposed to each other, an electrode structure in which flat plate-like positive electrodes and negative electrodes are alternately stacked (laminated type) ), An electrode structure in which a laminated belt-like positive electrode and negative electrode are wound (winding type), and the like.
• the current collector, the positive electrode, the positive electrode active material, the negative electrode, the negative electrode active material, and the electrolyte used for the nonaqueous electrolyte battery are not particularly limited, and conventionally known materials can be used in appropriate combination.
• the preparation method of the water-soluble polymer is shown below.
• Synthesis Example 1 Synthesis of polyimide resin A In a well-dried four-necked round bottom flask, 280.00 g of N-methylpyrrolidone (NMP) and 3,5-diaminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 3 , 5-DAB) 14.44 g (95 mmol) and 1,3-bis-3-aminopropyltetramethyldisiloxane (manufactured by Toray Dow Corning Co., Ltd., APDS) 1.24 g (5 mmol) were stirred under a nitrogen atmosphere. The solution was dissolved.
• NMP N-methylpyrrolidone
• 3,5-diaminobenzoic acid manufactured by Tokyo Chemical Industry Co., Ltd., 3 , 5-DAB
• APDS 1,3-bis-3-aminopropyltetramethyldisiloxane
• Synthesis Example 2 Synthesis of Polyimide Resin B Same as Synthesis Example 1 except that 14.44 g (95 mmol) of 3,5-DAB was changed to 9.88 g (95 mmol) of metaphenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., MDA). Thus, a polyimide resin B not including the structure represented by the general formula (1) was obtained. The weight average molecular weight was 23,000.
• Synthesis Example 3 Synthesis of Polyimide Resin C 14.44 g (95 mmol) of 3,5-DAB and 1.24 g (5 mmol) of APDS were converted to 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (AZ Electronic) Except for changing to 31.10 g (85 mmol) of trade name “AZ 6F-AP”, 6FAP) manufactured by Materials Co., Ltd. and 3.27 g (30 mmol) of 3-aminophenol (Tokyo Chemical Industry Co., Ltd., AMP).
• it has a structural unit represented by the general formula (2), all of R 5 are diamine residues represented by the general formula (1), and the terminal is 3-aminophenol.
• a sealed polyimide resin C was obtained. The weight average molecular weight was 24,000.
• Synthesis Example 4 Synthesis of polyimide resin D In a well-dried four-necked round bottom flask, 80.00 g of NMP, 3.66 g (10 mmol) of 6FAP, 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Kogyo Co., Ltd.) , 2.00 g (10 mmol) of a trade name “Kou DA”, 4,4′-DAE) was dissolved with stirring under a nitrogen atmosphere. Thereafter, this solution was cooled while stirring, and 14.28 g (20 mmol) of acid anhydride (TMDA) represented by the structural formula (4) synthesized by the method described in Synthesis Example 1 of JP-A-11-100503.
• TMDA acid anhydride
• Synthesis Example 5 Synthesis of polyimide resin E As in Synthesis Example 4, except that the amount of 6FAP added was changed to 1.83 g (5 mmol) and the amount of 4,4′-DAE added was changed to 3.00 g (15 mmol). has a structural unit represented by the general formula (2), to obtain a polyimide resin E 25 mole% of R 5 is a diamine residue represented by the general formula (1). The weight average molecular weight was 23,000.
• Synthesis Example 6 Synthesis of Polyimide Resin F The diamine was changed to 28.63 g (100 mmol) of 3,3′-dicarboxy-4,4′-diaminodiphenylmethane (trade name “MBAA” manufactured by Wakayama Seika Kogyo Co., Ltd.) Synthesis Example 1 except that the acid anhydride was changed to 44.40 g (100 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (manufactured by Daikin Industries, Ltd., 6FDA). In the same manner as above, a polyimide resin E having a structural unit represented by the general formula (2) and having all of R 5 as a diamine residue represented by the general formula (1) was obtained. The weight average molecular weight was 23,000.
• Synthesis Example 8 Synthesis of Polyamideimide Resin B The general formula was changed in the same manner as in Synthesis Example 6 except that the amount of 4,4′-DAE added was changed to 20.00 g (100 mmol) and 3,5-DAB was not used. Polyamideimide resin B not including the structure represented by (1) was obtained. The weight average molecular weight was 23,000.
• Synthesis Example 9 Synthesis of Polyamide Resin A
• 28.63 g (100 mmol) of MBAA was dissolved in 131.79 g of NMP while stirring under a nitrogen atmosphere. Then, this solution was ice-cooled with stirring, and a solution obtained by dissolving 20.30 g (100 mmol) of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd., IPC) in 15.00 g of NMP was kept at 30 ° C. or lower. While dripping. After dripping the whole quantity, it was made to react at 30 degreeC for 4 hours.
• Synthesis Example 10 Synthesis of polyamide resin B The diamine was changed to 7.61 g (50 mmol) of 3,5-DAB and 10.1 g (50 mmol) of 4,4′-DAE, and the addition amount of IPC was changed to 19.90 g (98 mmol). In the same manner as in Synthesis Example 9, except that the IPC 19.90 g (98 mmol) has a structural unit represented by the general formula (3), and 50 mol% of R 7 is represented by the general formula (1). A solid of polyamide resin B as a base was obtained. The weight average molecular weight was 21,000.
• Synthesis Example 11 Synthesis of Polyamide Resin C
• the diamine was changed to 32.96 g (90 mmol) of 6FAP and 1.52 g (10 mmol) of 3,5-DAB, and the acid chloride was terephthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd. , TPC) It has the structural unit represented by the general formula (3) in the same manner as in Synthesis Example 9 except that it is changed to 20.30 g (100 mmol), and all of R 7 is represented by the general formula (1).
• a solid of polyamide resin C which is a diamine residue was obtained.
• the weight average molecular weight was 23,000.
• Synthesis Example 12 Synthesis of Polyamide Resin D
• the diamine was changed to 22.90 g (80 mmol) of MBAA and 3.60 g (18 mmol) of 4,4′-DAE, and the acid chloride was changed to 2,6-naphthalenedicarboxylic acid chloride (Ihara Nikkei Chemical Industries). Co., Ltd., trade name “26NADOC”, NDCC) Except for changing to 25.31 g (100 mmol), it has the structural unit represented by the general formula (3) in the same manner as in Synthesis Example 9, and R 7
• the solid of polyamide resin D whose 82 mol% is a diamine residue represented by the general formula (1) was obtained.
• the weight average molecular weight was 22,000.
• Synthesis Example 14 Synthesis of Polyamide Resin F In the same manner as in Synthesis Example 9, except that the diamine was changed to 4,02′-DAE 20.02 g (100 mmol) and the acid chloride was changed to 20.30 g (100 mmol) of IPC. A solid of polyamide resin F not containing the structure represented by formula (1) was obtained. The weight average molecular weight was 23,000.
• Synthesis Example 15 Synthesis of Polyimide Resin G
• NMP 131.79 g was mixed with 3,3′-dicarboxy-4,4′-diaminodiphenylmethane (manufactured by Wakayama Seika Kogyo Co., Ltd.) 28.63 g (100 mmol) (trade name “MBAA”) was dissolved at room temperature with stirring under a nitrogen atmosphere.
• MBAA 3,3′-dicarboxy-4,4′-diaminodiphenylmethane
• the washed solid is dried in a 50 ° C. ventilated oven for 3 days, has a structural unit represented by the general formula (2), and 100 mol% of R 5 is represented by the general formula (1).
• a polyimide resin G was obtained.
• the weight average molecular weight was 28,000.
• Synthesis Example 16 Synthesis of Polyimide Resin H An acid anhydride was converted to bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) hereinafter, BOE) 24.82 g (except that the 100 mmol) in the same manner as in synthesis example 15, having a structural unit represented by the general formula (2), 100 mol% of R 5 is the general formula (1) The polyimide resin H which is a diamine residue represented by this was obtained. The weight average molecular weight was 30,000.
• Synthesis Example 17 Synthesis of Polyimide Resin J An acid anhydride was converted to 3- (carboxymethyl) -1,2,4-cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) Hereinafter, it has the structural unit represented by the general formula (2) in the same manner as in Synthesis Example 15 except that JPDA) is changed to 22.42 g (100 mmol), and 100 mol% of R 5 is represented by the general formula (1).
• the polyimide resin J which is a diamine residue represented was obtained, and the weight average molecular weight was 31,000.
• a method for preparing an aqueous resin solution containing a water-soluble polymer and a basic compound is shown below.
• the solubility of the water-soluble polymer in water was determined by visually observing the prepared aqueous solution.
• Resin aqueous solution 1 10.00 g of polyimide resin A obtained in Synthesis Example 1 and 0.94 g (0.02 mol) of sodium hydroxide were mixed, 100.00 g of water was added thereto, and the mixture was heated to 50 ° C. and stirred to obtain an aqueous resin solution. 1 was obtained.
• Resin aqueous solution 2-6, 9-12, 15, 17, 18, 20, 21, 23-31, 33-35 A resin aqueous solution was obtained in the same manner as the method for preparing the resin aqueous solution 1 except that the addition amount was changed as shown in Table 2.
• Table 2 DMAE represents dimethylaminoethanol, DMAB represents dimethylaminobutanol, TMAH represents tetramethylammonium hydroxide, and NEt 3 represents triethylamine.
• Resin aqueous solution 7 An attempt was made to prepare an aqueous resin solution in the same manner as in the preparation of the aqueous resin solution 1 except that sodium hydroxide was not added, but the polyimide resin did not dissolve.
• Resin aqueous solution 8 Although the polyimide resin A10.00g obtained in Synthesis Example 1 was changed to the polyimide resin B10.00g obtained in Synthesis Example 2, the production of the resin aqueous solution was attempted in the same manner as the resin aqueous solution 1 preparation method. It did not dissolve.
• Resin aqueous solution 13 1000.00 g of water was added to 10.00 g of the polyimide resin C obtained in Synthesis Example 3, and the mixture was heated to 50 ° C. and stirred without adding a basic compound. I didn't.
• Resin aqueous solution 14 The polyimide resin A10.00 g obtained in Synthesis Example 1 and calcium hydroxide 0.87 g (0.01 mol) are mixed, and 1000.00 g of water is added thereto, and the mixture is heated to 50 ° C. and stirred to obtain an aqueous resin solution. However, some polyimide resins were not dissolved.
• Resin aqueous solution 32 10.00 g of polyamide resin F obtained in Synthesis Example 14 and 2.45 g (0.06 mol) of sodium hydroxide were mixed, 49.81 g of water was added thereto, and the mixture was heated to 50 ° C. and stirred to obtain an aqueous resin solution. However, the polyamide resin was not dissolved.
• Resin aqueous solution 36 100.00 g of water was added to 10.00 g of carboxymethyl cellulose, and the mixture was stirred at 23 ° C. to obtain an aqueous resin solution 36.
• the solid content concentration is the total content of the water-soluble polymer and the basic compound in the aqueous solution.
• Thermal contraction rate (%) ⁇ (30 ⁇ d) / 30 ⁇ ⁇ 100
• the thermal shrinkage rate was measured for each temperature of 150 ° C., 160 ° C. and 200 ° C., and a value of less than 3% was evaluated as A, a value of 3% or more and 5% or less was B, and a value of greater than 5% was evaluated as C.
• Example 1 Alumina having an average particle size of 0.5 ⁇ m and the resin aqueous solution 1 were mixed so that polyimide resin A was 2.0 parts by mass with respect to 100 parts by mass of alumina to obtain a ceramic slurry. Furthermore, the concentration was adjusted with water so that the content of alumina in the ceramic slurry was 50% by mass.
• This ceramic slurry was mixed using a high-speed shearing type stirrer (DESPA, manufactured by Asada Tekko Co., Ltd.), and further dispersed using a continuous media disperser (NANO Grain Mill, manufactured by Asada Tekko Co., Ltd.).
• DESPA high-speed shearing type stirrer
• NANO Grain Mill manufactured by Asada Tekko Co., Ltd.
• a monomer mixture was prepared by mixing 78 parts by mass of 2-ethylhexyl acrylate, 19.8 parts by mass of acrylonitrile, and 2 parts by mass of methacrylic acid and 0.2 parts by mass of allyl methacrylate (AMA).
• a separate container 70 parts by mass of ion-exchanged water, 0.2 parts by mass of sodium dodecylbenzenesulfonate, 0.3 parts by mass of ammonium persulfate, and polyoxyethylene alkyl ether sulfate as an emulsifier (“Emar” manufactured by Kao Chemical Co., Ltd.) (Registered trademark D-3-D)) 0.82 parts by mass and polyoxyethylene lauryl ether (manufactured by Kao Chemical Co., Ltd., “Emulgen (registered trademark) -120”) 0.59 parts by mass were mixed. The phase portion was replaced with nitrogen gas, and the temperature was raised to 60 ° C. The aforementioned monomer mixture was added to the container, and emulsion polymerization was performed to prepare an aqueous dispersion of an acrylic resin.
• the aqueous dispersion of the acrylic resin is added to the ceramic slurry so that the acrylic resin is 2.0 parts by mass with respect to 100 parts by mass of alumina, and is mixed using a three-one motor with propeller blades.
• (II) A coating solution for formation was obtained.
• porous membrane (I) As the porous membrane (I), a polyethylene porous membrane (thickness 12 ⁇ m, air permeability 150 s / 100 cc Air, 150 ° C. heat shrinkage 80%) was prepared.
• the porous layer (II) -forming coating solution is applied to one side of the porous membrane (I) using a gravure coating machine, and dried at 50 ° C. for 1 minute.
• a porous layer (II) was formed on the nonaqueous electrolyte battery separator.
• the film thickness of the porous layer (II) in the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Examples 2 to 26 A coating solution was obtained in the same manner as in Example 1 except that the resin aqueous solution was changed as shown in Tables 3 and 4. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 27 Except for mixing alumina and the aqueous resin solution 1 so that the polyimide resin A is 5.0 parts by mass with respect to 100 parts by mass of alumina, the porous layer (II) is formed in the same manner as in Example 1. A coating solution was obtained. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 28 Except for mixing alumina and the aqueous resin solution 1 so that the polyimide resin A is 0.4 parts by mass with respect to 100 parts by mass of alumina, the porous layer (II) is formed in the same manner as in Example 1. A coating solution was obtained. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 29 A coating solution for forming the porous layer (II) was obtained in the same manner as in Example 1 except that the amount of the acrylic resin added was 5.0 parts by mass with respect to 100 parts by mass of alumina. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 30 A coating solution for forming the porous layer (II) was obtained in the same manner as in Example 1 except that the amount of the acrylic resin added was 0.5 parts by mass with respect to 100 parts by mass of alumina. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 31 Except for mixing alumina and the aqueous resin solution 1 so that the polyimide resin A is 5.5 parts by mass with respect to 100 parts by mass of alumina, the porous layer (II) is formed in the same manner as in Example 1. A coating solution was obtained. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 32 Except for mixing alumina and the aqueous resin solution 1 so that the polyimide resin A is 0.3 parts by mass with respect to 100 parts by mass of alumina, the porous layer (II) is formed in the same manner as in Example 1. A coating solution was obtained. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 33 A coating solution for forming a porous layer (II) was obtained in the same manner as in Example 1 except that the amount of the acrylic resin added was 5.5 parts by mass with respect to 100 parts by mass of alumina. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Example 34 A coating solution for forming the porous layer (II) was obtained in the same manner as in Example 1 except that the amount of the acrylic resin added was 0.4 parts by mass with respect to 100 parts by mass of alumina. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Examples 35-37 A coating solution for forming the porous layer (II) was obtained in the same manner as in Example 1 except that the resin aqueous solution was changed as shown in Table 4. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Comparative Examples 1-6, 9 A coating solution for forming the porous layer (II) was obtained in the same manner as in Example 1 except that the resin aqueous solution was changed as shown in Table 4. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Comparative Example 7 A coating solution for forming the porous layer (II) was obtained in the same manner as in Example 1 except that the aqueous resin solution was not added. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Comparative Example 8 A coating solution for forming the porous layer (II) was obtained in the same manner as in Example 1 except that the acrylic resin was not added. Using the obtained coating solution, a porous layer (II) was formed on the porous membrane (I) in the same manner as in Example 1 to obtain a nonaqueous electrolyte battery separator. The film thickness of the porous layer (II) of the obtained nonaqueous electrolyte battery separator was 4.0 ⁇ m.
• Tables 3 and 4 show the compositions of Examples 1 to 37 and Comparative Examples 1 to 9, and Tables 5 and 6 show the evaluation results.
• the content of the polymer is part by mass with respect to 100 parts by mass of the inorganic filler.
• Examples 1 to 37 which are non-aqueous electrolyte battery separators of the present invention, were excellent in evaluation results, but Comparative Examples 1 to 9, which are non-aqueous electrolyte battery separators outside the scope of the present invention, were inferior in evaluation results. As a result.

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